KR20030043909A - Organic-Inorganic Hybrid Light Emitting Devices (HLED) - Google Patents

Abstract

Silsesquioxane structural based organic-inorganic HLED materials are disclosed. This silsesquioxane compound comprises one or more, preferably a plurality of functional residue substituents selected from hole transport, electron transport and emitter residues and combinations thereof. Hybrid materials have OLED properties such as luminous efficiency, brightness, operating voltage, lifetime, and the like. An HLED device made of a polyhedral silsesquioxane HLED material is disclosed. Organic-inorganic HLED devices can include multiple layers of organic-inorganic light emitting materials with different functional residue substituents to balance charge transport and emission characteristics. HLED devices can be made of a monolayer of organic-inorganic hybrid luminescent materials that include hole transport, electron transport and emitter substituent moieties in a polyhedral silsesquioxane structure.

Description

Organic-Inorganic Hybrid Light Emitting Devices (HLED)}

Organic light emitting device (OLED) based flat panel displays have been intensively studied by hundreds of industrial and academic associations worldwide over the last decade. OLEDs offer excellent possibilities for thinner, more energy efficient displays with the same or better resolution and brightness compared to current liquid crystal display (LCD) technologies. OLEDs also offer high switching speeds, excellent viewing angles (> 160 °), red, green and blue (RGB) selectability, and do not require backlight to enable devices to be manufactured on flexible substrates. However, despite many research and development efforts on OLEDs, there is currently only one product commercially available using this technology. One obvious problem is the need for the development of new effective materials that meet the requirements of electronic devices.

The scientific basis for OLEDs depends on the ability of organic materials to emit light upon electrical stimulation. In this method, electrons and holes are injected into the organic material from the conducting electrode and dispersed through the organic thin film to form electron-hole pairs or excitons in the highly conjugated organic molecule or polymer layer. The excitons then recombine to form an excited state in the organic molecule. The excited state is then radiation decayed to emit photons. The wavelength of the light emitted depending on the organic polymer / molecule and its substituents may be of any color and may be of various colors, for example red, green, blue or a combination thereof.

For optimal performance it is important that the rates at which holes and electrons diffuse into the emitting layer are similar and preferably coincident. Therefore, a number of efforts have been made to optimize the transport of both holes and electrons to the emitting layer and also to prevent the capture of holes or electrons that have a disruptive effect in the device. Most recently, efforts have been made to incorporate organic molecules or polymers that promote the movement of holes or electrons in OLED devices. More recently, efforts have been made to incorporate organic molecular or monomeric units into the polymer system such that one organic unit promotes hole or electron conduction and the second organic unit promotes release. This electron tuning is designed to minimize the transport distance and maximize the hole / electron injection balance to improve the potential for radiation collapse rather than non-radiation collapse. A great deal of research remains in this area.

Early examples of organic electroluminescence are described in Pope et al., Pope, M .; Kallmann, H .; Magnante, P. J. Chem. Phys. 1962, 38, 2042 and exhibited blue light emission from single crystal anthracene using a very high voltage of about 400 V.

The next 20 years of development for OLED processing has involved the formation of light emitting thin films of organic compounds by vacuum deposition techniques (Vincett, PS; Barlow, WA; Hann, RA; Roberts, GG Thin Solid Films 1982, 94, 476). And limited to a reduction in drive voltage below 30 V, these single layer devices exhibited poor lifetime and luminous efficiency. In 1987, Tang and Van Slyke of Eastman Kodak discovered a method for manufacturing two-layer electroluminescent devices [Tang, C. W .; Van Slyke, S. A. Appl. Phys. Lett. 1987, 51, 913]. As shown in FIG. 1, an organic hole transport (HT) material 12 and an emitting material (EM) 14 are sandwiched between an indium tin oxide (ITO) anode 16 and a magnesium / silver alloy cathode 18 layer. The OLED device 10 was manufactured. The conventional potential source 20 was connected to the cathode 18 and the anode 16. The glass substrate 22 causes light to be emitted in the direction indicated by the arrow 24. The hole transport (HT) and release material (EM) used by Tang and Van Sleek are shown below.

The key to device performance is the layer structure order of cathode / emission-electron transport / hole transport / anode. These devices showed better brightness, efficiency and lifetime than anything reported at the time. The material shown in FIG. 1 was deposited on an indium tin oxide (ITO) coated glass to a thickness of about 25 nm by a vacuum sublimation process.

In 1990, Burroughs et al. Developed a polymer OLED device or PLED [Burroughs, J. H .; Bradley, D. D. C .; Brown, A. R .; Marks, R. N .; Mackay, K .; Friend, R. H .; Burn, P. L. Nature 1990, 347, 539]. In 1992 Braun et al. Discovered that poly (p-phenylenevinylene) (PPV) and its derivatives electroluminesce both green and red light when present between ITO and aluminum electrodes [Braun, D. ; Gutafson, D .; McBranch, D .; Heeger, A., J. J. Appl. Phys., 1992, 72, 546].

This study is important because PPV polymers can be deposited by a more cost effective spin coating process than vacuum sublimation. Spin coating is also advantageous for coating a wider area. As a result of these pioneering examples, hundreds of OLED and PLED substrate papers have been reported by researchers around the world using two common material depositions:

1. vacuum sublimation of molecular species, and

2. Dip, spin and spray coating or printing of oligomeric or polymeric materials

Each method has the following advantages and disadvantages.

Vacuum sublimation works well only on relatively low molecular weight (MW) compounds (<300 g / mol). Such compounds should be purified to purity> 99.99% by sublimation or column chromatography prior to deposition to achieve good light emission efficiency and device lifetime. Vacuum sublimation allows for highly accurate control of multilayer arrangements and film thicknesses, both of which are advantageous in OLED processing. The disadvantage of vacuum sublimation is that it requires a very expensive device and is limited to deposition on fewer surface areas than can be coated using spin coating. In addition, device performance is disadvantageous because some sublimation compounds tend to crystallize over time. To prevent premature crystallization the present compounds are designed to have high glass transition temperatures (Tg) and to have substituents which minimize or prevent crystallization.

Generally dip coating, spin coating, spray coating and printing techniques can be used for the deposition of oligomeric and polymeric materials. They allow precise film thickness control, a wide area range, and are relatively inexpensive compared to vacuum sublimation. Multilayer arrangements are only possible if the deposition layer is designed to have curable functionalities for subsequent crosslinking, or to have different solubility to prevent re-dissolution during further coating. For example, current OLED polymer technology uses a water soluble prepolymer PPV (shown below), which is heat cured after deposition to become insoluble [Li, X. C .; Moratti, S. C. Semiconducting Polymers as Light-Emitting Materials; Wise, D. L., Wnek, G. E., Trantolo, D. J., Cooper, T. M. and Gresser, J. D., Ed., 1998].

Early luminescent properties of polymer based OLEDs were often inferior to their molecular counterparts. This is partly because it is difficult to obtain high purity materials (99.99%) (polydispersity, end groups, residual solvents and by-products such as HCl, catalysts, etc.) required for effective devices. However, recent studies have shown that carefully purified polymers have similar or better properties than their molecular counterparts.

Some important parameters to consider when devising new materials for practical devices include the following.

1) Deposition Methods—Spin, spray, dip coating, and ink (bubble) jet printing are typically more cost effective than vacuum sublimation. Therefore, the luminescent material can preferably be used for spraying, spin coating, dip coating and / or printing methods.

2) Material Molecular Structure-The material should be designed to prevent or minimize crystallization and / or aggregation known to result in inferior device properties.

3) Color Tuning and Color Purity-The luminescent material should be designed to provide red, green and blue (RGB) electroluminescence for electrochromic devices. They should be easily purified to ≧ 99.99% purity.

4) Increased device efficiency, brightness and lifetime-to provide a commercial device, the material must be> 2% external quantum efficiency (2 photon emission per 100 injected electrons), <500 V / m2 operation and emission at 5 V. Half-life> 10,000 hours (approximately equal to 10 h / day for 3 years, 6 days / week).

5) Fabrication of Effective Device Structures—The most commonly reported designs are shown in FIG. 1. The cathode is generally prepared by vacuum deposition of Ag / Mg, Ca or Al. Typically, cathodes with low work functions provide good initial device performance. That is, Ca <Al / Li / Ag / Mg <Al. However, Al is generally selected as the cathode material because Ca, Ag and Mg are more sensitive to oxidation. The anode is typically a commercially available ITO coated glass. The study indicated that the final device performance is directly related to the ITO surface properties, so be very careful when selecting an ITO anode. In contrast, poly (aniline) (PANI) and poly (2,3-ethylenedioxy) thiophene (PEDOT) were used as anode materials in both ITO deposited glass and flexible Mylar® substrates.

From the substrate, it can be easily purified to high purity, has a high Tg, has little tendency to crystallize or agglomerate, can be processed by spin coating, dip coating or printing, and can be used for thermal, oxidation, hydrolysis and electrolysis. It will be appreciated that there is a need in the art for OLED materials that are highly resistant, can be easily modified to have suitable properties such as stability, electroluminescent efficiency, solubility, etc., have a low operating voltage and relatively easy color tuning. .

FIELD OF THE INVENTION The present invention relates to compositions used to make light emitting devices, and more particularly, to organic-inorganic compounds wherein the hole transporting, electron transporting and emitting compounds are made from light emitting compositions covalently bonded to polyhedral silsesquioxanes. A hybrid light emitting device (HLED).

1 is a schematic illustration of a typical OLED device arrangement.

2A is a schematic illustration of an HLED device within the scope of the present invention that includes a monolayer of HLED material with integrated hole transport, electron transport, and emitter material properties.

2B is a schematic illustration of an HLED device within the scope of the present invention that includes separate electron transport, emission and hole transport layers of the HLED material.

3 is a graph of solution and thin film photoluminescence versus wavelength for the hybrid material described in Example 2. FIG.

4 is a graph of current (A) and light emission (cd / m 2) versus voltage for a two layer device made of the inorganic-organic HLED material of Example 2. FIG.

<Detailed Description of the Preferred Embodiments>

The present invention relates to novel organic-inorganic HLED materials in which the organic component is covalently bonded to the silsesquioxane inorganic (or organometallic) unit. The organic-inorganic HLED silsesquioxane material has the formula

<Formula>

(RSiO _1.5 ) _n

Where

n is typically in the range of 6 to 12, but can be in the range of values as large as 100,

R is selected from functional groups including hole transport (HT), electron transport (ET) and emitter material (EM).

Hybrids can be synthesized from core polyhedral silsesquioxane intermediates with reactive substituents capable of reacting with functional groups having HT, ET or EM properties. Some hybrids can also be synthesized using direct sol-gel synthesis with R-Si (OCH ₂ CH ₃ ) ₃ as starting material.

Presently preferred embodiments within the scope of the present invention rely on polyhedral octahedrons or cubic silsesquioxanes. Silsesquioxanes have a skeletal skeleton found in crystalline forms of silica and certain zeolites [Bartsch, M .; Bornhauser, P .; Calzaferri, GJ Phys. Chem. 1994, 98, 2817]. This structure may represent a building block in which subsequent chemistry is used to produce a hybrid having the desired LED properties as described above. Such structures are readily produced from inexpensive starting materials in yields ranging from> 90% to 30%. Hard skeletons provide many attractive properties pioneered by Feher et al. [Feher, FJ; Newman, DA; Walzer, JF, J. Am. Chem. Soc., 1989, 111, 1741] The only model of the silica surface is the zeolite model by Cazaferri et al. [Bartsch et al., Described above] and the only sol-gel precursor by Klemperer et al. [Agaskar] , PA; Day, VW; Klemperer, WG, J. Am. Chem. Soc., 1987, 109, 5545], and other groups for various applications. These materials, in particular (HSiO _1.5 ) _n series, were intensively studied by Agaskar (Agaskar, PA; J. Am. Chem. Soc., 1989, 111, 6858), Agaskar, PA , Inorg. Chem., 1992, 30, 2708, Agaskar, PA, Colloids and Surfaces, 1992, 63, 131 and Agaskar, PA, Synth.React.Inorg.Met.-Org.Chem., 1992, 20, 483]. Routes for the relevant [(R (CH ₃ ) ₂ SiO) SiO _1.5 ] ₈ and [(R (CH ₃ ) ₂ SiO) SiO _1.5 ] _6/10 cubic are described in Hasegawa, I .; Motojima, S., J. Organomet. Chem., 1992, 373 and Hasegawa, I., J. of So1-Gel Sci. and Tech., 1994, 2, 127 and German Patent DE 3837397, respectively.

In addition, functionalized cubic silsesquioxanes in which R is H, OSi (CH ₃ ) ₂ H, CH = CH ₂ , epoxy and methacrylate have incorporated individual nano-structures and suitable properties defined within the organic matrix. Hybrids can be provided (Sellinger, A .; Laine, RM; Chu, V .; Viney, C., J. Polymer Sci., Part A, Polymer Chemistry, 1994, 32, 3069), Sellinger, A .; Laine, RM, Macromolecules, 1996, 26, Sellinger, A .; Laine, RM, Chem. Mater., 1996, 8, 1592; and Laine, RM; Zhang, C., J. Organomet. Chem., 1996, 521, 199].

The combination of silsesquioxanes and electroluminescent functionalities provides many unique beneficial properties. This is based on coupling known and novel OLED functional groups with defined electronic properties (ie electron transport, hole transport or emission properties) with the silsesquioxanes shown below.

Where

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are selected from hole transporting, electron transporting or releasing materials and curable moieties as defined below.

Examples of organic-inorganic HLED materials substituted with individual hole transport, electron transport and emission moieties are illustrated below. Those skilled in the art will appreciate that other HLED materials can be prepared with differentiated hole, electron transport and emission moieties.

This HLED material has several advantages over the molecules and polymers currently described in the literature. For example, this HLED material may have a molecular weight of 3000 g / mol or more, and thus may be used in spraying, dip and / or spin coating or printing methods more cost effectively than vacuum sublimation. Other advantages described below include high temperature stability, ease of purification, high density of HT, ET and EM residues, and prevention of crystallization and aggregation formation.

As mentioned above, HLED materials can be synthesized from polyhedral silsesquioxane intermediates with reactive substituents capable of reacting with functional groups having HT, ET or EM properties. Several possible reactions that can be used for this are outlined below. Such reactions include, but are not limited to, high yield metal catalyzed silicon hydride, Heck, Suzuki and Buchwald-Hartwig amination chemistries. In each reaction, it will be understood that one reactant will contain the silsesquioxane intermediate and the other will contain the desired functionality.

The platinum catalyzed silicon hydride additions of silicon hydride and double and triple bonds are shown below.

The palladium catalyzed hex reaction of vinyl groups and activated aromatic compounds is shown below.

Where

X is Cl, Br, I, triflate or other leaving group.

The palladium catalyzed Suzuki reaction of halophenyl and activated aromatic compound is shown below.

Where

X is Cl, Br, I, triflate or other leaving group.

The palladium catalyzed Buchwald-Hartwig amination reaction of the activated aromatic compound with the aromatic amine is shown below.

Some hybrids can be synthesized using direct sol-gel synthesis with R-Si (OCH ₂ CH ₃ ) ₃ as starting material, as shown below.

Wherein R is a hole transport moiety, an electron transport moiety, an emitter moiety or a curable group.

Since some ET groups are sensitive to the acid or base reaction conditions used in the sol-gel process, the process may not be suitable for preparing ET functionalized silsesquioxane materials, with previous reaction methods being preferred.

This chemistry is direct and versatile and can provide photocurable and / or thermoset materials for multiple coating performance. The double bonds remaining from the reaction of Si-H and triple bonds allow each layer to be deposited immediately after curing into an insoluble network. For example, 1) a cube containing HT, ET and EM residues in a single cubic (such as compound 3) can be synthesized in a single step deposition process (FIG. 2A), or 2) HT, ET or Individual cubic (such as compounds 2A-2C) containing only EM residues can be synthesized (FIG. 2B), or 3) any combination of these possibilities can be chosen.

2A shows an HLED device 30 that includes a monolayer of HLED material 32 with integrated hole transport, electron transport, and emitter material properties. Such HLED materials can be used to make devices in a single step deposition process. Those skilled in the art will appreciate that other HLED materials can be prepared with emission / hole transport residues, emission / electron transport residues or hole / electron transport residue combinations. 2B is a schematic illustration of an HLED device 40 within the scope of the present invention that includes separate hole transport 42, emission 44, and electron transport 46 layers of HLED material.

Hybrids described in the present invention can be purified by conventional polymer methods such as precipitation in non-solvents. In contrast to polymers, however, silsesquioxane based hybrids can be purified by flash column chromatography to provide materials having an ideal purity ≧ 99.99% for LED materials. Since the cubic material may comprise up to 40% by weight of silica, its thermal, hydrolysis and mechanical properties (eg wear resistance) are superior to conventional OLED materials. The resulting material is amorphous and transparent, and therefore has little tendency to crystallize over time. In addition, since hard rod-like HT, ET and release moieties are branched from the three-dimensional central core, there is little opportunity for alignment and aggregation, minimizing the chance of excimer formation (charge capture) in the device. Highly efficient chemistry and the resulting monodisperse spherical structures (sometimes called dendrimers or starburst molecules) allow precise control of functional groups (curing), process parameters (viscosities), color tuning, electronic and optical properties, and material morphology. do. HLEDs can be designed hydrophobic by fluoroalkyl groups, as shown in compound 4 below, because adsorbed water is known to reduce OLED device life and efficiency.

Where

The substituent R is preferably selected from hole transport, electron transport and emitter residues.

Although compound 4 appears to have four substituents R, those skilled in the art will understand that the type and number of substituents may vary. In other words, the octahedral silsesquioxane structure based organic-inorganic HLED material may contain 1 to 8 functional substituents, which substituents may be the same or different.

The following are examples of typical electron transport moieties that can be chemically attached and / or used in the cubic range within the scope of the present invention (ET-HLED). Exemplary compounds are given for illustration only. Those skilled in the art will understand that other known and novel electron transport moieties may be used in the present invention, including aromatic pyridine, quinoline, triazole, oxadiazole, dicyanoimidazole, cyano aromatic, imino aromatic and triazine Or organic compounds comprising a combination thereof.

The following are examples of typical hole transport moieties that can be chemically attached and / or used in the cubic range within the scope of the present invention (HT-HLED). Exemplary compounds are given for illustration only. Those skilled in the art will understand that other known and novel hole transport moieties may be used in the present invention, including organic compounds including aromatic phosphines, aromatic amines, thiophenes (polythiophenes), silanes (polysilanes) and derivatives This includes, but is not limited to.

The following are examples of typical emitter residue substituents that may be used for HLED materials within the scope of the present invention. Exemplary compounds are given for illustration only. Those skilled in the art will appreciate that other known and novel release moieties may be used in the present invention.

Where

R and R 'are H, C, O, N, S, Si, Ge, fluoroalkane, fluorosilylalkane and the like,

n is selected to optimize the release properties and is typically in the range of 1 to 100, more preferably 1 to 20.

The compounds shown above are examples of materials that can be used to make HLEDs. This is merely to illustrate HLED materials within the scope of the present invention and is not intended to limit the present invention to the illustrated compounds.

The present invention includes methods for synthesizing and characterizing silsesquioxane structure based organic-inorganic HLED materials. These hybrid materials can have the combined advantages of both molecules and polymers, and thus can be used in the field of OLEDs. Silsesquioxane compounds comprise one or more, preferably multiple functional residue substituents, in a single compound. Functional substituents are preferably selected from hole transport (HT), electron transport (ET) and emitter (EM) residues and combinations thereof. This can optimize OLED properties such as luminous efficiency, brightness, operating voltage, lifetime, high density HT, ET and EM residues and the like.

The organic-inorganic HLED silsesquioxane material has the formula

<Formula>

(RSiO _1.5 ) _n

Where

n typically ranges from 6 to 12 with respect to the separation cage structure, but n may be a greater value (up to about 100) in the extended polymer silsesquioxane structure,

R is selected from a number of functional groups including hole transport, electron transport and emissive materials.

Hybrids can be synthesized from continuous core polyhedral silsesquioxane intermediates with various reactive substituents capable of reacting with functional groups having HT, ET or EM properties. Examples of typical reactive substituents of silsesquioxane intermediates include, but are not limited to, hydrogen, vinyl, phenyl, substituted phenyl, stilbenyl and substituted stilbenyl, wherein the phenyl substituents include halo, amino, hydroxyl, vinyl, Unsaturated alkyl, haloalkyl, silyl and the like. Some hybrids can also be synthesized using direct sol-gel synthesis with R-Si (OCH ₂ CH ₃ ) ₃ as starting material.

The organic-inorganic HLED material having the octahedral silsesquioxane structure has the following structure.

Where

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent hole transport residues, electron transport residues, emitter residues and curable residues (epoxy, methacrylate, stryl, vinyl, Propazil and combinations thereof, including but not limited to).

The hybrid material preferably comprises one or more HT, ET or EM residues. Curable groups are included to benefit the manufacture of multilayer devices but are not necessary in single layer devices.

The present invention includes organic-inorganic HLED devices made of the HLED materials described above. Such devices are typically based on anodes containing high work function metals, metal alloys or metal oxides, cathodes containing low work function metals or metal alloys, the silsesquioxane structures described above and physical and electrical to the anodes and cathodes. It comprises a layer of organic-inorganic light emitting material connected with. The organic-inorganic HLED device is preferably made of a transparent substrate such as glass or transparent plastic. The anode is preferably selected from gold, silver, copper, indium tin oxide (ITO), fluorine tin oxide (FTO) or other transparent conductive oxide or polymeric material. Gold, silver and copper layers of less than about 50 nm are translucent and useful as anode materials. The cathode is selected from calcium, magnesium, lithium, sodium, aluminum and alloys thereof. The cathode may also be selected from a mixture of halogen salts of Group IA metals (Li, Na, K, Rb, Cs) with calcium, magnesium, lithium, sodium and aluminum. For example, commercially available Al / Li alloys (98.5% Al / 1.5% Li) Al are relatively stable in air and have a work function similar to Ca. Similarly, LiF, CsF and other salts can reduce the work function upon deposition at the Al / organic interface.

The organic-inorganic HLED device may comprise a multilayer of organic-inorganic light emitting materials. Each layer may be based on a luminescent material having different functional residue substituents selected from hole transport, electron transport and emitter residues. For example, an HLED device may include a layer with hole transport substituents, a layer with electron transport substituents, but the hole and / or electron transport layer (s) also act as emission components. Other substituents can be included to provide the desired functional or physical properties such as improved hydrophobicity, adhesion properties and color tuning dyes for HLED materials. HLED materials can also be designed to include various properties such as balanced electron and hole transport as well as emission properties.

Organic-inorganic HLED devices can be made of a monolayer of organic-inorganic luminescent materials that include hole transport, electron transport and emitter substituent residues on the silsesquioxane structure. HLED devices can also be fabricated in multiple layers including balanced emission, hole transport, and electron transport layers to provide the desired luminescent properties.

The following examples are given to illustrate various embodiments within the scope of the present invention. It is given for the purpose of illustration only, and the following examples should not be understood to cover all or all of the embodiments within the scope of the invention.

Example 1

Product from the reaction of octavinylsilsesquioxane with 2- (4-bromophenyl) -5- (1-naphthyl) -1,3,4-oxadiazole

Octavinylsilsesquioxane (1 g, 1.57 mmol), 2- (4-bromophenyl) -5- (1-naphthyl) -1,3,4-oxadiazole (3.32 g, 9.46 mmol), Palladium acetate (0.021 g, 0.095 mmol) and tris (o-tolyl) phosphine (0.072 g, 0.238 mmol) were added to a 25 mL Schlenk flask equipped with a stir bar, condenser, vacuum and argon gas source. . The contents of the flask were emptied and refilled with argon three times. Dry toluene (50 mL) and dry acetonitrile (10 mL) are added, then triethylamine (1.45 mL, 10.4 mmol) is added and the solution is heated to 100 ° C. for 48 hours until thin layer chromatography indicates completion of the reaction. Stirred at. The solution was cooled to rt and poured into dichloromethane (200 mL). 5% HCl (100 mL) was added and the organic layer was extracted three times with brine (100 mL). The organic layer was separated, dried over sodium sulfate and the volume reduced to a tan solid (90% yield). Samples can be purified by column chromatography using a 95/5 hexanes / ethyl acetate system. Alternatively, the solution was poured into 300 mL of methanol and the precipitate was obtained by filtration. The powder was redissolved in THF or dichloromethane, filtered through a 0.45 μm Teflon membrane (Pall), the powder precipitated again in methanol, collected by filtration and dried. Palladium dibenzylideneacetone [Pd ₂ (dba) ₃ ], tri-t-butylphosphine (1/1 molar ratio) and N, N-dicyclohexylmethylamine were respectively palladium acetate and tris (o-tolyl) phosphine And triethylamine. Electronic reagents allow milder reaction conditions, ie room temperature and shorter reaction time (8 hours) than 100 ° C. Size exclusion chromatography (SEC) showed no starting material and M _n = 2270 g / mol (actual 2252 g / mol) and polydispersity index (PDI) 1.10. Proton NMR was consistent with the title material, and differential scanning calorimetry (DSC) showed glass transition (Tg) = 125 ° C.

Example 2

Product from the reaction of octavinylsilsesquioxane and 1- (m-tolyl-phenylamino) -1 '-(p-bromophenyltolylamino) biphenyl

This material was prepared using the method of example 1 to yield a yellow solid in 85% yield. The dilute solution photoluminested very strongly in the presence of long wavelength light (about 360 nm) which gave bright blue light. The excitation wavelength of 366 nm was used to obtain a solution photoluminescence spectrum maximum of 488 nm. The photoluminescence results for both the solution and the thin film are shown in FIG. 3. Size exclusion chromatography (SEC) showed no starting material and M _n = 4920 g / mol (actual 4750 g / mol) and polydispersity index (PDI) 1.05. Proton NMR was consistent with the title material, and differential scanning calorimetry (DSC) showed glass transition (Tg) = 152 ° C. Thermal gravity analysis (TGA) in air provided a ceramic yield of 11.2% (theoretical ceramic yield = 10.1%).

The organic-inorganic HLED material prepared herein was made into a two layer device, which is illustrated in FIG. 1. Referring to FIG. 1, the cathode layer 18 is an Al / Li (98.5 / 1.5) alloy, the layer 14 is an emitter (EM) tris (8-hydroxyquinolinate) aluminum (Alq ₃ ), layer (12) is the organic-inorganic HLED material produced herein, anode layer 16 is indium tin oxide (ITO), layer 22 is glass. 4 is a graph of current (A) and light emission (cd / m 2) versus voltage for the manufactured device.

Example 3

Product from the reaction of octavinylsilsesquioxane with 9,9-di-n-butyl-2-bromofluorene

This product was prepared using the method of example 1 and obtained a yellow solid in 91% yield. Size exclusion chromatography (SEC) showed no starting material and M _n = 2825 g / mol (actual 2015 g / mol) and polydispersity index (PDI) 1.15. Proton NMR was consistent with the title material, and differential scanning calorimetry (DSC) showed glass transition (Tg) = 102 ° C. Thermal gravity analysis in air (TGA) gave a ceramic yield of 26% (theoretical ceramic yield = 23%).

Example 5

Preparation of α- (bromo) -ω- (4-methoxyphenyl) -poly-2,7- (9,9-dioctylfluorene)

This monobrominated polymer is described in D. Marzitzky, M. Klapper, K. Mullen; Macromolecules, Vol. 32, no. 25, 1999, 8685]. 2-bromo-9,9-di-n-octylfluoreneboric acid (1.0 g, 1.98 mmol), potassium fluoride (0.40 g, 6.93 mmol), palladium acetate (0.004 g, 0.020 mmol), 2-dicyclohexyl Phospanyl-biphenyl (0.014 g, 0.040 mmol) was added to a 50 mL Schlenk tube in a glove box. This tube was transferred to a Schlenk line and 7 mL of dry toluene and 7 mL of DMAc were added. The solution was stirred for 2 to 24 hours at room temperature and the polymer was capped by adding excess 4-bromoanisole (1.2 mL) at 80 ° C. The solution was stirred for additional 8 h at 80 ° C. and then precipitated in 200 mL of methanol. The precipitate was dried, finely ground, stirred with 5% HCl for 1 hour, filtered, rinsed with methanol and dried. The dried polymer was redissolved in a minimum amount of dichloromethane and again reprecipitated in 200 mL of methanol to give a dry polymer in 65% yield. Molecular weight 4900 g / mol was obtained by NMR end group analysis of methoxy protons. GPC showed PDI 1.20-1.50 depending on MW 1200-6000 g / mol and reaction time.

Example 6

Preparation of Polyfluorene Star Polymers with a Central Silsesquioxane Core

Α- (bromo) -ω- (4-methoxyphenyl) -poly-2,7- (9,9-dioctylfluorene) (1 g, 0.20 mmol) from Example 5, octavinylsilses Quioxane (0.025 g, 3.92 x 10 ^-5 mol), palladium acetate (0.002 g, 0.01 mmol) and tris (o-tolyl) phosphine (0.007 g, 0.02 mmol) were added to a stir bar, condenser, vacuum and argon gas source. To a fitted 25 mL Schlenk flask. The contents of the flask were emptied and refilled with argon three times. Dry toluene (10 mL) and dry acetonitrile (or THF, dioxane) (2 mL) were added, followed by triethylamine (0.035 mL, 0.25 mmol) and the solution was stirred at 100 ° C. for 48 h. . The solution was cooled to room temperature and poured into cold methanol (20 mL) to precipitate a yellow solid. This solid was isolated by filtration, redissolved in dichloromethane (2 mL) and reprecipitated in methanol. The GPC results were in agreement with the expected structure. Alternatively, palladium dibenzylideneacetone [Pd ₂ (dba) ₃ ], tri-t-butylphosphine and N, N-dicyclohexylmethylamine are respectively palladium acetate, tris (o-tolyl) phosphine and triethyl It may be used instead of an amine. Electronic reagents allow for milder reaction conditions, ie 50 ° C. rather than 100 ° C.

The present invention can be implemented in other specific forms without departing from its structure, methods and other essential features as broadly described herein and claimed below. The described embodiments are for illustration only and should not be understood as being limited thereto. Therefore, the scope of the invention is indicated by the claims rather than the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (30)

An organic-inorganic HLED material comprising a silsesquioxane structure having one or more functional moiety substituents selected from hole transport, electron transport and emitter residues. The organic-inorganic HLED material of claim 1, wherein the silsesquioxane structure comprises a plurality of functional residue substituents selected from hole transport, electron transport and emitter material residues. The organic-inorganic HLED material of claim 1, wherein the silsesquioxane structure comprises a plurality of different functional residue substituents selected from hole transport, electron transport and emitter material residues. The organic-inorganic HLED material of claim 3, wherein the functional residue substituent comprises one or more emitter residues and one or more other functional residues selected from hole transport and electron transport residues. The organic-inorganic HLED material of claim 1, wherein the electron transport moiety is selected from aromatic pyridine, quinoline, triazole, oxadiazole, dicyanoimidazole, triazine, cyano aromatic, imino aromatic, or a combination thereof. . The organic-inorganic HLED material of claim 1, wherein the hole transport moiety is selected from aromatic phosphines, aromatic amines, thiophenes, silanes or combinations thereof. The organic-inorganic HLED material of claim 1, wherein the release moiety is selected from the following functional residue substituent groups. Where R and R 'are H, C, O, N, S, Si, Ge, fluoroalkane and fluorosilylalkanes, n is from 1 to 100. An organic-inorganic HLED material comprising a polyhedral silsesquioxane structure having the structure Where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R _At least one of ₇ and R ₈ is a hole transport residue, an electron transport residue or an emitter residue. The organic-inorganic HLED material of claim 8, wherein at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is selected from a solubilizer and a curable group. 10. The organic-inorganic HLED material of claim 9, wherein the solubilizer is selected from fluoroalkanes and fluorosilylalkanes. The organic-inorganic HLED material according to claim 9, wherein the curable group is selected from epoxy, methacrylate, stryl, vinyl, propazyl and combinations thereof. The compound of claim 8, wherein at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is hydrogen, vinyl, phenyl, substituted phenyl, vinyl phenyl and substituted vinyl phenyl Wherein the phenyl substituent comprises halo, amino, hydroxyl vinyl, vinyl, unsaturated alkyl, and halo alkyl. An organic-inorganic HLED material having the formula <Formula> (RSiO _1.5 ) _n Where n ranges from 6 to 100, R may be the same or different and is selected from hole transport residues, electron transport residues, emitter residues, curable residues and solubilization residues, and one or more R substituents are hole transport, electron transport or emitter residues. The organic-inorganic HLED material of claim 13, wherein n is in the range of 6-12. The organic-inorganic HLED material of claim 13, wherein the curable moiety is selected from epoxy, methacrylate, stryl, vinyl, propazyl and combinations thereof. The organic-inorganic HLED material of claim 13, wherein the solubilization moiety is selected from fluoroalkanes and fluorosilylalkanes. Anodes containing high work function metals or metal alloys, Cathodes containing low work function metals or metal alloys, Layer of organic-inorganic luminescent material comprising silsesquioxane structure having one or more functional residue substituents selected from hole transport, electron transport and emitter residues and electrically connected to the anode and cathode Organic-inorganic HLED device comprising a. 18. The organic-inorganic HLED device of claim 17, further comprising a transparent substrate in the manufacture of the device. 18. The organic-inorganic HLED device of claim 17, wherein the anode is selected from gold, silver, copper, fluorine tin oxide (FTO) and indium tin oxide (ITO). 18. The organic-inorganic HLED device of claim 17, wherein the anode is selected from poly (aniline) (PANI) and poly (2,3-ethylenedioxy) thiophene (PEDOT). 18. The organic-inorganic HLED device of claim 17, wherein the cathode is selected from calcium, magnesium, lithium, sodium, aluminum and alloys thereof. 18. An organic-inorganic HLED device according to claim 17, wherein the cathode is selected from a mixture of halogen salts of alkaline earth metals and calcium, magnesium, lithium, sodium and aluminum. 18. The organic-inorganic HLED device of claim 17, further comprising at least one additional layer of organic-inorganic light emitting material. The organic-inorganic HLED device of claim 17, wherein the organic-inorganic light emitting material comprises a plurality of different functional residue substituents selected from hole transport, electron transport and emitter residues. 18. The organic-inorganic HLED device of claim 17 comprising a monolayer of organic-inorganic light emitting material comprising hole transport, electron transport and emitter substituent moieties. 18. An organic-inorganic HLED device according to claim 17, comprising a layer of organic-inorganic light emitting material having emitter substituents and a layer of organic-inorganic light emitting material having electron transport substituents. 18. The organic-inorganic HLED device of claim 17, comprising a layer of organic-inorganic light emitting material with emitter substituents and a layer of organic-inorganic light emitting material with hole transport substituents. 18. An organic-inorganic HLED device according to claim 17, wherein the electron transport moiety is selected from aromatic pyridine, quinoline, triazole, oxadiazole, dicyanoimidazole, triazine, cyano aromatic, imino aromatic or combinations thereof. . 18. The organic-inorganic HLED device of claim 17, wherein the hole transport moiety is selected from aromatic phosphines, aromatic amines, thiophenes, silanes or combinations thereof. 18. The organic-inorganic HLED device of claim 17, wherein the release moiety is selected from the following functional moiety substituent groups. Where R and R 'are H, C, O, N, S, Si, Ge, fluoroalkane and fluorosilylalkanes, n is from 1 to 100.